CN117024697A - Polyurethane sponge with high air permeability and preparation method thereof - Google Patents

Polyurethane sponge with high air permeability and preparation method thereof Download PDF

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Publication number
CN117024697A
CN117024697A CN202311002217.1A CN202311002217A CN117024697A CN 117024697 A CN117024697 A CN 117024697A CN 202311002217 A CN202311002217 A CN 202311002217A CN 117024697 A CN117024697 A CN 117024697A
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China
Prior art keywords
polyurethane sponge
parts
foaming
air permeability
diphenylmethane diisocyanate
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CN202311002217.1A
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Chinese (zh)
Inventor
王峰
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Guangdong Dopda High Tech Materials Co ltd
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Guangdong Dopda High Tech Materials Co ltd
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Priority to CN202311002217.1A priority Critical patent/CN117024697A/en
Publication of CN117024697A publication Critical patent/CN117024697A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/63Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of polyurethane sponge, and discloses a high-air-permeability polyurethane sponge and a preparation method thereof. The polyurethane sponge with high air permeability is prepared from polyether polyol, polymer polyol, modified diphenylmethane diisocyanate, stabilizer, catalyst, composite additive and water, has excellent air permeability and heat dissipation function, and can meet the application of the sponge with higher performance in daily necessities.

Description

Polyurethane sponge with high air permeability and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane sponge, in particular to a high-air-permeability polyurethane sponge and a preparation method thereof.
Background
The conventional polyurethane sponge is a conventional foaming technology at present, and is mainly formed by reacting isocyanate and polyether polyol through relevant catalysts and foaming agents. The common polyurethane sponge is of a porous (honeycomb) chain structure, and membranous substances generated by reaction are covered among meshes of each structure, so that the air permeability and heat dissipation performance of the laminated structure are poor. Affecting the development of polyurethane sponge in the application field.
The prior high-air-permeability sponge is usually subjected to subsequent demolding treatment on the common polyurethane sponge, so that the air permeability of the sponge accords with the application. However, the cost of the demolding process is high, the yield of the product after demolding is low, and the bonding strength between the polyurethane sponge after demolding and other materials is low, so that the practicability of the polyurethane sponge is affected. Therefore, there is a need in the art to develop a polyurethane sponge with high air permeability.
Disclosure of Invention
In view of the above, the invention provides a high-permeability polyurethane sponge and a preparation method thereof, which are used for solving the problems of complex preparation process, high cost and low yield of the high-permeability sponge in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a high-air-permeability polyurethane sponge which comprises the following raw materials in parts by weight: 70-90 parts of polyether polyol, 15-30 parts of polymer polyol, 30-40 parts of modified diphenylmethane diisocyanate, 0.5-1.5 parts of stabilizer, 0.1-0.5 part of catalyst, 5-15 parts of composite additive and 1-5 parts of water.
Preferably, the NCO content of the modified diphenylmethane diisocyanate is 32-40% and the purity is 98-99.9 wt%.
Preferably, the stabilizer is polyether siloxane; the catalyst is stannous octoate or dibutyl tin dilaurate.
Preferably, the composite additive comprises sodium dodecyl sulfate, citric acid, glycerol and genipin.
Preferably, the mass ratio of the sodium dodecyl sulfate to the citric acid to the glycerol to the genipin is 0.2-0.6: 0.05 to 0.08:0.05 to 0.06:1.
the invention also provides a preparation method of the high-air-permeability polyurethane sponge, which comprises the following steps:
polyether polyol, polymer polyol, modified diphenylmethane diisocyanate, stabilizer, catalyst, composite additive and water are mixed and foamed to obtain the polyurethane sponge with high air permeability.
Preferably, the specific steps of the mixing are as follows: firstly, polyether polyol, polymer polyol and modified diphenylmethane diisocyanate are mixed, and then a stabilizer, a catalyst, a composite additive and water are added.
Preferably, the temperature at which the polyether polyol, the polymer polyol and the modified diphenylmethane diisocyanate are mixed is 18 to 20 ℃.
Preferably, the foaming temperature is 70-90 ℃; the stirring speed of the foaming is 2000-3000 r/min; the foaming pressure is 30-70 bar; the foaming speed is 4-6 m/min.
Preferably, after the foaming is finished, the product obtained by foaming is cured; the curing time is 20-24 hours.
Compared with the prior art, the invention has the following beneficial effects:
the polyurethane sponge with high air permeability is prepared from polyether polyol, polymer polyol, modified diphenylmethane diisocyanate, stabilizer, catalyst, composite additive and water, has excellent air permeability and heat dissipation function, and can meet the application of the sponge with higher performance in daily necessities.
Detailed Description
The invention provides a high-air-permeability polyurethane sponge which comprises the following raw materials in parts by weight: 70-90 parts of polyether polyol, 15-30 parts of polymer polyol, 30-40 parts of modified diphenylmethane diisocyanate, 0.5-1.5 parts of stabilizer, 0.1-0.5 part of catalyst, 5-15 parts of composite additive and 1-5 parts of water.
According to the invention, the polyurethane sponge with excellent air permeability is prepared by combining other raw materials through the advantages of optimizing the pore structure and enriching the pore quantity of the composite additive.
In the present invention, the polyether polyol is used in an amount of preferably 72 to 85 parts, more preferably 75 to 80 parts; the amount of the polymer polyol is preferably 16 to 28 parts, more preferably 18 to 25 parts; the amount of the modified diphenylmethane diisocyanate is preferably 32 to 38 parts, more preferably 35 to 37 parts; the amount of the stabilizer is preferably 0.8 to 1.2 parts, more preferably 0.9 to 1.1 parts; the catalyst is preferably used in an amount of 0.2 to 0.4 part, more preferably 0.3 part; the amount of the compound additive is preferably 8 to 13 parts, more preferably 9 to 12 parts; the amount of water to be used is preferably 2 to 4 parts, more preferably 3 parts.
In the present invention, the modified diphenylmethane diisocyanate is preferably a modified diphenylmethane diisocyanate having an NCO content of 32 to 40% and a purity of 98 to 99.9% by weight, and more preferably a basf Lupranate MI modified MDI.
In the present invention, the stabilizer is preferably polyether siloxane; the catalyst is preferably stannous octoate or dibutyltin dilaurate, more preferably stannous octoate.
In the present invention, the complex additive preferably includes sodium dodecyl sulfate, citric acid, glycerin, and genipin.
In the invention, the mass ratio of the sodium dodecyl sulfate to the citric acid to the glycerol to the genipin is preferably 0.2-0.6: 0.05 to 0.08:0.05 to 0.06:1, more preferably 0.3 to 0.5:0.06 to 0.07:0.05:1.
the invention also provides a preparation method of the high-air-permeability polyurethane sponge, which comprises the following steps:
polyether polyol, polymer polyol, modified diphenylmethane diisocyanate, stabilizer, catalyst, composite additive and water are mixed and foamed to obtain the polyurethane sponge with high air permeability.
In the invention, the specific steps of mixing are as follows: firstly, polyether polyol, polymer polyol and modified diphenylmethane diisocyanate are mixed, and then a stabilizer, a catalyst, a composite additive and water are added.
In the present invention, the temperature at which the polyether polyol, the polymer polyol and the modified diphenylmethane diisocyanate are mixed is preferably 18 to 20 ℃, more preferably 19 ℃.
The invention can ensure that the polyether polyol, the polymer polyol and the modified diphenylmethane diisocyanate cannot lose effectiveness before the reaction and ensure the smooth proceeding of the later foaming by controlling the mixing temperature of the polyether polyol, the polymer polyol and the modified diphenylmethane diisocyanate.
In the present invention, the foaming temperature is preferably 70 to 90 ℃, and more preferably 75 to 85 ℃; the stirring speed of the foaming is preferably 2000-3000 r/min, more preferably 2500-2800 r/min; the pressure of the foaming is preferably 30 to 70bar, more preferably 40 to 60bar; the speed of the foaming is preferably 4 to 6m/min, more preferably 5m/min.
In the invention, after the foaming is finished, curing the product obtained by foaming; the curing time is preferably 20 to 24 hours, more preferably 22 to 23 hours.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The polyether polyol used in the following examples was the Medium sea Shell polyether polyol ED56-200; the polymer polyol used was purchased from the Yangzhou chemical company, inc.; the stabilizer used is TEGOPREN 5840 silicone polyether, a company of Di Add technology development (Shanghai); the modified diphenylmethane diisocyanate used was basf Lupranate MI modified MDI.
Example 1
70 parts of medium sea shell polyether polyol ED56-200, 15 parts of American Dow PL 1881G polymer polyol and 30 parts of Basoff Lupranate MI modified MDI are added into a foaming machine to be mixed at a temperature of 19 ℃, then 0.5 part of TEGOPREN 5840 siloxane polyether, 0.1 part of stannous octoate, 3.3 parts of sodium dodecyl sulfate, 0.4 part of citric acid, 0.3 part of glycerol, 6 parts of genipin and 3 parts of water are added, mixed, and then the mixture is foamed in the foaming machine, the foaming temperature is kept at 75 ℃, the stirring speed of foaming is 2000r/min, the foaming pressure is 40bar, and the foaming speed is 5m/min. And curing the obtained product at room temperature for 20 hours after foaming is finished to obtain the polyurethane sponge with high air permeability.
Example 2
80 parts of medium sea shell polyether polyol ED56-200, 15 parts of American Dow PL 1881G polymer polyol and 39 parts of Basoff Lupranate MI modified MDI are added into a foaming machine to be mixed at a temperature of 19 ℃, then 0.8 part of TEGOPREN 5840 siloxane polyether, 0.1 part of stannous octoate, 3.3 parts of sodium dodecyl sulfate, 0.4 part of citric acid, 0.3 part of glycerol, 6 parts of genipin and 3 parts of water are added, mixed, and then the mixture is foamed in the foaming machine, the foaming temperature is kept at 80 ℃, the stirring speed of foaming is 2500r/min, the foaming pressure is 40bar, and the foaming speed is 5m/min. And curing the obtained product at room temperature for 21 hours after foaming is finished to obtain the polyurethane sponge with high air permeability.
Example 3
85 parts of a medium sea shell polyether polyol ED56-200, 15 parts of an American Dow PL 1881G polymer polyol and 35 parts of a Basoff Lupranate MI modified MDI were added to a foaming machine and mixed at a temperature of 19 ℃, after which 0.8 part of a TEGOPREN 5840 silicone polyether, 0.3 part of dibutyltin dilaurate, 3.3 parts of sodium dodecyl sulfate, 0.4 part of citric acid, 0.3 part of glycerol, 6 parts of genipin and 3 parts of water were added and mixed, and then the mixture was foamed in the foaming machine, wherein the foaming temperature was kept at 90 ℃, the stirring speed of foaming was 2500r/min, the foaming pressure was 50bar, and the foaming speed was 5m/min. And curing the obtained product at room temperature for 21 hours after foaming is finished to obtain the polyurethane sponge with high air permeability.
The high air permeability polyurethane sponges obtained in examples 1 to 3 were examined for air permeability and porosity, and the examination methods and results were as follows.
The detection method comprises the following steps: the air permeability of the high air permeability polyurethane sponges obtained in examples 1 to 3 was measured by using a TQ-01 type air permeability tester for sponges (porous elastic materials) according to the national standard "measurement of air permeability of high polymer porous elastic materials" (GB/T10655-2003), and the porosities of the high air permeability polyurethane sponges obtained in examples 1 to 3 were measured, and the measurement results are shown in Table 1.
Table 1 breathability and porosity of the highly breathable polyurethane sponges obtained in examples 1 to 3
Sample of Example 1 Example 2 Example 3
Air permeability (mm/s) 64.32 75.98 72.18
Porosity (%) 92 95 93
As can be seen from Table 1, the high-breathability polyurethane sponge obtained by the invention has good breathability, is greatly improved compared with the breathability of the existing polyurethane sponge, and has a high void ratio.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The polyurethane sponge with high air permeability is characterized by comprising the following raw materials in parts by weight: 70-90 parts of polyether polyol, 15-30 parts of polymer polyol, 30-40 parts of modified diphenylmethane diisocyanate, 0.5-1.5 parts of stabilizer, 0.1-0.5 part of catalyst, 5-15 parts of composite additive and 1-5 parts of water.
2. The high permeability polyurethane sponge according to claim 1, wherein the modified diphenylmethane diisocyanate has an NCO content of 32 to 40% and a purity of 98 to 99.9% by weight.
3. The high permeability polyurethane sponge of claim 2, wherein the stabilizer is polyether siloxane; the catalyst is stannous octoate or dibutyl tin dilaurate.
4. A highly breathable polyurethane sponge according to any one of claims 1 to 3 wherein said composite additives include sodium dodecyl sulphate, citric acid, glycerol and genipin.
5. The high-breathability polyurethane sponge according to claim 4, wherein the mass ratio of sodium dodecyl sulfate, citric acid, glycerin and genipin is 0.2-0.6: 0.05 to 0.08:0.05 to 0.06:1.
6. the method for preparing a polyurethane sponge with high air permeability according to any one of claims 1 to 5, comprising the steps of:
polyether polyol, polymer polyol, modified diphenylmethane diisocyanate, stabilizer, catalyst, composite additive and water are mixed and foamed to obtain the polyurethane sponge with high air permeability.
7. The method for preparing the polyurethane sponge with high air permeability according to claim 6, wherein the specific steps of mixing are as follows: firstly, polyether polyol, polymer polyol and modified diphenylmethane diisocyanate are mixed, and then a stabilizer, a catalyst, a composite additive and water are added.
8. The method for preparing a highly breathable polyurethane sponge according to claim 7, wherein the temperature at which said polyether polyol, polymer polyol and modified diphenylmethane diisocyanate are mixed is 18 to 20 ℃.
9. The method for preparing a high air permeability polyurethane sponge according to claim 7 or 8, wherein the foaming temperature is 70-90 ℃; the stirring speed of the foaming is 2000-3000 r/min; the foaming pressure is 30-70 bar; the foaming speed is 4-6 m/min.
10. The method for producing a highly breathable polyurethane sponge according to claim 9, wherein after the foaming is completed, the foamed product is cured; the curing time is 20-24 hours.
CN202311002217.1A 2023-08-09 2023-08-09 Polyurethane sponge with high air permeability and preparation method thereof Pending CN117024697A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070299151A1 (en) * 2004-11-05 2007-12-27 Guelcher Scott A Degradable Polyurethane Foams
CN107057011A (en) * 2016-02-10 2017-08-18 赢创德固赛有限公司 The mattress and/or cushion of anti-aging and low emission
CN107118543A (en) * 2017-05-25 2017-09-01 德清舒华泡沫座椅有限公司 A kind of space pillow
CN108610464A (en) * 2018-05-22 2018-10-02 广汉市新鸿海绵有限公司 A kind of dedicated high rigidity shaping sponge of sofa and preparation method thereof
CN109134809A (en) * 2018-08-07 2019-01-04 苏州思德新材料科技有限公司 A kind of pore type polyurethane foam material and preparation method thereof
CN115322322A (en) * 2022-09-14 2022-11-11 浙江东洋佳嘉海绵制品有限公司 High-air-permeability sponge and manufacturing method thereof
US20230106042A1 (en) * 2021-10-01 2023-04-06 Hyundai Transys Inc. Method of manufacturing polyurethane filter foam

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070299151A1 (en) * 2004-11-05 2007-12-27 Guelcher Scott A Degradable Polyurethane Foams
CN107057011A (en) * 2016-02-10 2017-08-18 赢创德固赛有限公司 The mattress and/or cushion of anti-aging and low emission
CN107118543A (en) * 2017-05-25 2017-09-01 德清舒华泡沫座椅有限公司 A kind of space pillow
CN108610464A (en) * 2018-05-22 2018-10-02 广汉市新鸿海绵有限公司 A kind of dedicated high rigidity shaping sponge of sofa and preparation method thereof
CN109134809A (en) * 2018-08-07 2019-01-04 苏州思德新材料科技有限公司 A kind of pore type polyurethane foam material and preparation method thereof
US20230106042A1 (en) * 2021-10-01 2023-04-06 Hyundai Transys Inc. Method of manufacturing polyurethane filter foam
CN115322322A (en) * 2022-09-14 2022-11-11 浙江东洋佳嘉海绵制品有限公司 High-air-permeability sponge and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
侯惠民: "车用非金属材料的透气度检测(二)", 汽车工艺与材料, no. 10, pages 33 - 34 *

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Application publication date: 20231110